Epoxy resins toughened with in situ azide–alkyne polymerized polysulfones

To simultaneously improve the fracture toughness and heat resistance of a cured toughened epoxy resin along with a reduction in its viscosity during the mixing process, two novel polysulfone‐type polymers are synthesized via azide–alkyne polymerization for use as toughening agents. The epoxy resin toughened with these polymers by in situ azide–alkyne polymerization during the cure process, which shows excellent processibility and based on the significantly lower viscosity (61 and 62 cP) during epoxy mixing process than that of commonly commercial polyethersulfone (PES, 127,612 cP). The novel polysulfone‐type polymer toughened epoxy resin showed the advantage in excellent fracture toughness than the PES toughened epoxy. In addition, the glass transition temperature of the novel polysulfone‐type polymer toughened epoxy resin is similar to that of the neat one (～230 °C) and does not decrease, which implies excellent heat resistance of the toughened epoxy. These phenomena can be attributed to the formation of semi‐interpenetrating polymer networks comprising the epoxy network and the linear polysulfone‐type polymers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45790.     

A novel spin-finishing method for antistatic modification of polyester fiber. Surface reaction onto amine-containing copoly(amide-ethers) blended with polyester fiber

Copoly(amide-ethers) containing two types of tertiary amine units were made as antistatic modifiers for poly(ethylene terephthalate) (PET) fibers. The filaments of the copolymers were melt-spun and reacted with three alkylating agents in order to quaternize the tertiary amine into a sulfo-betaine, a carbobetaine, and an ammonium ion. The apparent electric resistivity of the filaments was greatly reduced by this reaction, being in the range of 10⁶ to 10⁸ Ω/cm. However, because these quaternized copolymers incurred decomposition during blend spinning with PET, a blend PET fiber containing one type of copoly(amide-ether) was melt-spun and subjected to quaternization of the amino groups as well as to surface crosslinking with various alkylating and epoxy agents. The quaternized blend fibers obtained showed improved antistatic properties compared with the original blend fiber. Particularly, the fibers crosslinked with epoxy compounds were found to have the best antistatic properties that had ever been attained with this type of modification. The antistatic properties were retained even after dyeing, because both hydrophilic and ionic groups had been effectively immobilized on the surface. Since this quaternization and crosslinking could be conducted on-line with spinning and drawing within a short reaction time, this modification technique is called “spin-finishing method”, which should be superior to the conventional methods in terms of cost performance and productivity.     

A facile antistatic modification of polyester fiber based on ion-exchange reaction of sulfonate-modified polyester and various cationic surfactants

A new technique for imparting antistatic properties to poly(ethylene terephthalate) (PET) fiber has been developed. In this technique, blend polyester fibers containing poly(ethylene terephthalate/5-sulfoisophthalate) (SIP-PET) were prepared by blend spinning and then treated with various cationic surfactants in the process of dyeing. The surfactants could effectively be immobilized on the fiber as the counter cations of the sulfonate groups of the 5-sulfoisophthalate (SIP) units and aid the release of static electrons formed in the fiber. Thus, the half-life time (t_1/2) of leakage of static charge and the surface resistivity (Rs) of the blend PET fibers became much lower after treating. The best result was obtained with a methylated quaternary ammonium salt of a stearylamine-ethylene oxide (EO) adduct or hydrochloride of a laurylamine-EO adduct as the surfactant of which the number of EO units was around ten. Even after five washing cycles the t_1/2 value of the fibers treated with these surfactants was kept lower than 30 s with the Rs value maintained in the order of 10¹³ Ω cm^-2. Therefore, the present technique could be useful for practical production of polyester fibers with “semi-permanent” antistatic properties which can be recovered by re-treatment even if they were lost.     

Enantioselective α‐Alkylation of Benzylideneamino tert‐Butyl Malonates by Phase‐Transfer Catalysis

A new enantioselective synthetic method for the synthesis of α,α‐dialkylmalonates with a quaternary carbon center was developed via α‐alkylation of prochiral malonates by phase‐transfer catalysis (PTC). Asymmetric α‐alkylation of benzylideneamino tert‐butyl α‐methylmalonates under phase‐transfer catalytic conditions in the presence of (S,S)‐3,4,5‐trifluorophenyl‐NAS bromide afforded the corresponding α,α‐dialkylmalonates in high yields (up to 97%) with excellent enantioselectivities (up to 98% ee). The products were then selectively hydrolyzed to chiral malonic monoacids under basic, acidic, or catalytic hydrogenation conditions.

     

Wet oxidation of wastewater containing hydrocarbons by novel supported Pd catalysts

Pd catalysts supported on TiO₂, ZrO₂, ZSM-5, MCM-41 and activated carbon were used in catalytic wet oxidation of hydrocarbons such as phenol, m-cresol and m-xylene. It was found that the Pd/TiO₂ catalyst was highly effective in the wet oxidation of hydrocarbon. The activities of catalysts with various hydrocarbon species, catalyst support, oxidation state of catalyst performed in a 3-phase slurry reactor show that reaction on Pd surface is more favorable than that in aqueous phase and that the active site is oxidized Pd in catalytic wet air oxidation of hydrocarbons. Based on the experimental results, a plausible reaction mechanism of wet oxidation of hydrocarbons catalyzed over Pd/TiO₂ catalyst was proposed. This catalyst is superior to other oxide catalysts because it suppressed the formation of hardly-degradable organic intermediates and polymer.     

Rapid and efficient deoxygenation of sulfoxides to sulfides with tantalum(V) chloride/sodium iodide system

TaCl₅/NaI system converts a wide range of sulfoxides to the corresponding sulfides in high yields with short reaction times, under mild conditions. It is worth mentioning that this protocol is chemoselective and tolerates various functional groups (such as –Br, –Cl, –OCH₃, –CHO, and –NO₂) and double bond.     

Formation process of core‐shell microparticles by solute migration during drying of homogenous composite droplets

Particle formation process during spray drying profoundly impacts particle morphology and microstructure. This study experimentally investigated the formation of core‐shell‐structured microparticles by one‐step drying of composite droplets made of Eudragit^® RS (a polycationic acrylic polymer in nanoparticle form) and silica sol. The formation of an incipient surface shell was monitored using single droplet drying technique, and the freshly formed shell was recovered for subsequent analyses. Adding silica to RS precursor increased the shell formation time and altered the properties of the incipient shell from water‐dispersible to nondispersible. The incipient shell formed from RS/silica droplets with mass ratios of 1.5%:1.5% and 0.5%:2.5% showed ingredient segregation with a preferential accumulation of RS, similar to the shell region of dried microparticles. After shell formation, excess silica sol in the liquid phase could flow inward, producing a dense core. This mobility‐governed solute migration would be useful for constructing core‐shell microparticles using other precursor systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3297–3310, 2017     

Nano-assembly of intertwining lamellae of opposite bending senses in poly(ethylene oxide) co-crystallizing with poly(p-vinyl phenol)

Strongly interacting amorphous poly(p-vinyl phenol) (PVPh) was added into semi-crystalline poly(ethylene oxide) (PEO) at 20 wt.% to generate dendritic lamellae of alternating birefringence colors, which intertwine roughly in the radial directions as periodic stripes. Optical and atomic-force microscopy analyses are performed on revealing lamellae assembly in highly dendritic PEO spherulites by crystallizing PEO/PVPh (80/20) at crystallization temperature (T _c ) equals to 45 °C. The lamellae of two opposite colors in the same PEO spherulite quadrant are exactly of same geometry (of elongated plates, each being 0.2 μm in width and 2–5 μm in length), but they fan out +/?45^o, respectively, as they grow away from the radial direction. The opposite colored-lamellae are radiating out in radial directions, interweaving each other to display alternating colors in radial alignment. However, such alternating colors can also be similarly seen in ring-banded spherulites in many polymers. The results presented in this study have demonstrated that the lamellae of alternating birefringent colors cannot only be seen in banded spherulites, but also in spherulites with radial dendrites.     

A prioritization method for replacement of water mains using rank aggregation

Pipe breaks in municipal water distribution networks may cause serious damage economically and socially. Existing methods for replacement scheduling of pipes do not provide practical indicators for replacing an individual deteriorated pipe. This work formulates the selection problem as the decision of preference ordering or ranking and proposes a bipartite ranking-based approach. The suggested approach also considers loss from broken pipes in terms of the costs associated with broken water main and its repair. We use rank aggregation method to integrate multiple ranks into replacement order of water mains. The suggested framework prioritizes current pipe sections for replacement based on the aggregated ranks. Multiple ranks given by the reliability of water pipe sections are aggregated and a cost effective policy for pipe replacement is derived.     

A reaction kinetic study of CO<Subscript>2</Subscript> gasification of petroleum coke,coals and mixture

Characteristics of Char-CO₂ gasification were compared in the temperature range of 1,100–1,400 °C using a thermogravimetric analyzer (TGA) for petroleum coke, coal chars and mixed fuels (Petroleum coke/coal ratios: 0, 0.25, 0.5, 0.75, 1). The results showed that reaction time decreased with increasing gasification temperature, BET surface area and alkali index of coal. Mixed fuels composed of petroleum coke/coal exhibited reduced activation energies. Modified volumetric reaction model and shrinking core model might be suitably matched with experimental data depending on coal type and petroleum coke/coal ratio. Rate equations were suggested by selecting gas-solid reaction rate models for each sample that could simulate CO₂ gasification behavior.